CN101811725B - Cage-shaped nano zinc oxide and preparation method thereof - Google Patents
Cage-shaped nano zinc oxide and preparation method thereof Download PDFInfo
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- CN101811725B CN101811725B CN2010100301443A CN201010030144A CN101811725B CN 101811725 B CN101811725 B CN 101811725B CN 2010100301443 A CN2010100301443 A CN 2010100301443A CN 201010030144 A CN201010030144 A CN 201010030144A CN 101811725 B CN101811725 B CN 101811725B
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Abstract
The invention discloses cage-shaped nano zinc oxide and a preparation method thereof, and relates to a method for preparing zinc oxide. The cage-shaped nano zinc oxide material has a multilayer cage-shaped structure consisting of nano zinc oxide granules. The preparation method for the cage-shaped nano zinc oxide comprises the following process steps: (1) dissolving zinc acetate and glucose in 80 milliliters of deionized water, ultrasonically treating the solution for 10 minutes to form cleared solution, then transferring the cleared solution to a polytetrafluoroethylene inner container, putting the inner container into a stainless steel autoclave, and hermetically reacting the solution; (2) putting the autoclave into an oven to perform thermal reaction for 12 hours, naturally cooling a reaction product to room temperature after the reaction to obtain black powder, then centrifugally washing the black powder for multiple times by using deionized water respectively, washing the black powder by using ethanol to remove a little amount of carbon-containing substance in the product, and drying the washed black powder at the temperature of 60 DEG C; and (3) putting the powder into a muffle furnace and calcining the powder to form the cage-shaped nano zinc oxide material. The cage-shaped nano zinc oxide material is used in the fields of photocatalyst, optical devices, sensors, solar cells, medicinal capsules and the like.
Description
Technical field:
The present invention relates to zinc oxide preparation method, particularly a kind of cage-shaped nano zinc oxide and preparation method thereof.
Background technology:
It is " the most promising material of 21 century " that nano material is described as, and zinc oxide is as a kind of important II-IV semiconductor material, it at room temperature energy gap be 3.37eV, have bigger exciton bind energy (～60eV).Nano-ZnO is compared with common ZnO, because of its distinctive surface effects, volume effect, quantum effect and dielectric confinement effect etc., in catalysis, optics, magnetics, sensing and terms of mechanics have obtained using widely, and particularly it to organic catalyzed degradation effect, makes it obtain important use in a lot of fields such as pottery, chemical industry, electronics, optics, biology, medicine in the ultraviolet region.Zinc oxide has variforms such as nanotube, nanometer rod, nano belt, nano-rings, nanocages, nanometer spiral and superstructure, is one of the most various member of structure in the nano material.And different structures has different specific purposes, makes that the pattern of ZnO and structure control are significant.But because the polarity of the different crystal faces of zinc oxide has very big-difference, zinc oxide is easy to grow along [001] direction, thereby form the unidimensional nano structure of zinc oxide, so all be by adding certain tensio-active agent usually, inductor, the perhaps pattern of adjusting zinc oxide under the non-aqueous solvent condition.Owing to added organic solvent or directed agents in the reaction system, caused pollution to a certain degree, and post-processed is more loaded down with trivial details, simultaneously because the use of organic solvent makes its preparation cost increase greatly, thereby has limited the large-scale application of nano zinc oxide material.
(Xi Wang such as Wang Xi for example, Peng Hu, Yuan Fangli, and Iingjie Yu.Preparation and Characterization of ZnO Hollow Spheres and ZnO-Carbon Composite Materials Using Colloidal Carbon Spheres as Templates, J.Phys.Chem.C, 2007,111:6706-6712) prepared the hollow Nano zinc oxide sphere as template with the carbon ball, have good effect for the photodegradation methylene blue.But this method be by the carbon ball as template, can only obtain hollow zinc oxide sphere, and the nano zinc oxide material that can not get having the multilayer cage structure.
Summary of the invention:
The purpose of this invention is to provide a kind of nano-ZnO preparation that can obtain the multilayer cage structure.The preparation method of cage-shaped nano zinc oxide of the present invention.The technical scheme of cage-shaped nano zinc oxide of the present invention is that a kind of cage-shaped nano zinc oxide material is characterized in that: the cage-shaped nano zinc oxide material is the multilayer cage structure that nano granular of zinc oxide constitutes.The cage wall of described multilayer cage structure is that the Zinc oxide particles of 20-40nm is formed by diameter, the hole diameter≤30nm on the cage wall, and outermost cage wall thickness is not more than 60nm.The preparation method of cage-shaped nano zinc oxide of the present invention is, it is characterized in that following processing step is arranged: (1) is that 0.1mol/L zinc acetate and concentration are that the glucose of 0.1-0.5mol/L is dissolved in the 80ml deionized water with concentration, the molar concentration rate of zinc acetate and glucose is 1-4: 1, ultrasonic 10 minutes, after forming settled solution, after transfer is put in the polytetrafluoroethylliner liner, put into stainless steel autoclave, sealed reaction, (2) aforesaid reaction vessel is placed under 160-190 ℃, carry out hydro-thermal reaction in the baking oven, reacted 12 hours, and naturally cooled to room temperature after the reaction, obtain the black powder, deionized water carries out repeatedly centrifuge washing respectively then, and use washing with alcohol, to remove a spot of carbonaceous material in the product, dry down at 60 ℃ then, (3) above-mentioned powder is put into retort furnace, be warming up to by the speed of 5 ℃/min that calcining naturally cooled to room temperature after 3 hours under 500 ℃ of atmospheric environments, promptly make cage-shaped nano zinc oxide material of the present invention.The present invention has the multilayer cage structure compared with the prior art and the technology cost is low and the remarkable advantage of friendly environment.
Description of drawings:
Accompanying drawing is a multilayer cage shape zinc oxide material sem photograph of the present invention.
Embodiment:
Embodiment 1:
Take by weighing Zn (CH
3COO)
22H
2O and glucose are dissolved in the 80ml deionized water, and ultrasonic 10 minutes, form clear soln, wherein the acetic acid zinc concentration is 0.1mol/L, the concentration of glucose is 0.1mol/L.The mol ratio of zinc salt and glucose is Zn
2+/ C
6H
12O
6=1.Put into stainless steel autoclave after changing over to this settled solution in the polytetrafluoroethylliner liner, sealed reactor, hydro-thermal reaction is 12 hours under 160 degree conditions, after being cooled to room temperature, with the black powder that obtains, carry out repeatedly centrifuge washing with deionized water respectively, and use washing with alcohol, to remove a spot of carbonaceous organism in the product.The dry composite precursor that obtained zinc oxide and carbon in 12 hours under the 60 degree conditions afterwards; The precursor for preparing is placed retort furnace, be warming up to 500 degree, be incubated 3 hours, naturally cool to room temperature then, obtain having the nanometer Zinc oxide powder material of multilayer cage structure with the speed of 5 ℃/min.Final sample is done scanning electronic microscope, transmission electron microscope and X ray to be observed.The result shows the introducing by glucose, the pattern of zinc oxide all becomes nanometer spherical or elliposoidal structure, and has a multiwalled cage structure, nano particle and hole have constituted the cage wall, the surface of nanocages smooth, and transparency is lower, the diameter of outermost layer cage is about 500 nanometers, the thickness of cage wall is about 60 nanometers, the cage wall thickness of formed cage structure, and surperficial poroid feature is not obvious.
Embodiment 2:
Raw material that uses and reactor are with embodiment 1, and wherein the acetic acid zinc concentration is 0.1mol/L, and the concentration of glucose is 0.2mol/L.The mol ratio of zinc salt and glucose is Zn
2+/ C
6H
12O
6=1.Put into stainless steel autoclave after changing over to this settled solution in the polytetrafluoroethylliner liner, sealed reactor, hydro-thermal reaction is 12 hours under 180 degree conditions, after being cooled to room temperature, with the black powder that obtains, carry out repeatedly centrifuge washing with deionized water respectively, and use washing with alcohol, with a spot of carbonaceous organism in the product of place to go.The dry composite precursor that obtained zinc oxide and carbon in 12 hours under the 60 degree conditions afterwards; The precursor for preparing is placed retort furnace, be warming up to 500 ℃, be incubated 3 hours, naturally cool to room temperature then, obtain having the nanometer Zinc oxide powder material of multilayer cage structure with the speed of 5 ℃/min.Final sample is done scanning electronic microscope, transmission electron microscope and X ray to be observed.The result shows the introducing by glucose, the pattern of zinc oxide all becomes nanometer spherical or elliposoidal structure, and has a multiwalled cage structure, nano particle and hole have constituted the cage wall, the surface of nanocages coarse, and transparency is lower, the diameter of outermost layer cage is about 600 nanometers, the thickness of cage wall is about 30 nanometers, and the cage wall of formed cage structure is thin, and surperficial poroid feature is obvious.
Embodiment 3:
Raw material that uses and reactor are with embodiment 1, and wherein the acetic acid zinc concentration is 0.1mol/L, and the concentration of glucose is 0.4mol/L.The mol ratio of zinc salt and glucose is Zn
2+/ C
6H
12O
6=4.Put into stainless steel autoclave after changing over to this settled solution in the polytetrafluoroethylliner liner, sealed reactor, hydro-thermal reaction is 12 hours under 190 degree conditions, after being cooled to room temperature, with the black powder that obtains, carry out repeatedly centrifuge washing with deionized water respectively, and use washing with alcohol, with a spot of carbonaceous organism in the product of place to go.The dry composite precursor that obtained zinc oxide and carbon in 12 hours under the 60 degree conditions afterwards; The precursor for preparing is placed retort furnace, be warming up to 500 ℃, be incubated 3 hours, naturally cool to room temperature then, obtain having the nanometer Zinc oxide powder material of multilayer cage structure with the speed of 5 ℃/min.Final sample is done scanning electronic microscope, transmission electron microscope and X ray to be observed.The result shows the introducing by glucose, the pattern of zinc oxide all becomes nanometer spherical or elliposoidal structure, and has a multiwalled cage structure, nano particle and hole have constituted the cage wall, the surface irregularity of nanocages, transparency height, the diameter of outermost layer cage is between the 400-600 nanometer, the thickness of cage wall is about 20 nanometers, and the cage wall of formed cage structure is thin, and surperficial poroid feature is more obvious.But compare with result in 2 with embodiment 1, the distortion of cage structure is apparent in view, and the diameter of cage is homogeneous not too.
Multilayer cage-shaped nano zinc oxide material, the cage wall is made up of nano granular of zinc oxide, have flourishing pore passage structure, the size of nanocages and cage wall thickness are controlled, and it can be widely used in light and urges fields such as agent, optics, transmitter, solar cell, pharmaceutical capsule.
Claims (2)
1. cage-shaped nano zinc oxide material is characterized in that: the cage-shaped nano zinc oxide material is the multilayer cage structure that nano granular of zinc oxide constitutes; The cage wall of described multilayer cage structure is that the Zinc oxide particles of 20-40nm is formed by diameter, the hole diameter≤30nm on the cage wall, and outermost cage wall thickness is not more than 60nm.
2. method for preparing cage-shaped nano zinc oxide material as claimed in claim 1, it is characterized in that following processing step is arranged: (1) is that 0.1mol/L zinc acetate and volumetric molar concentration are that the glucose of 0.1-0.5mol/L is dissolved in the 80ml deionized water with volumetric molar concentration, the molar concentration rate of zinc acetate and glucose is 1-4: 1, ultrasonic 10 minutes, after forming settled solution, after transfer is put in the polytetrafluoroethylliner liner, put into stainless steel autoclave, sealed reaction, (2) aforesaid reaction vessel is placed under 160-190 ℃, carry out hydro-thermal reaction in the baking oven, reacted 12 hours, and naturally cooled to room temperature after the reaction, obtain the black powder, carry out repeatedly centrifuge washing with deionized water respectively then, and use washing with alcohol, to remove a spot of carbonaceous material in the product, dry down at 60 ℃ then, (3) powder that above-mentioned steps (2) is obtained is put into retort furnace, be warming up to by the speed of 5 ℃/min that calcining naturally cooled to room temperature after 3 hours under 500 ℃ of atmospheric environments, promptly make the cage-shaped nano zinc oxide material.
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| CN102701267A (en) * | 2012-06-04 | 2012-10-03 | 兰州大学 | Preparation method for ZnO nanosphere with yolk-eggshell structure |
| CN103318941B (en) * | 2012-09-12 | 2014-09-03 | 上海工程技术大学 | Synthetic method of porous ZnO three-dimensional superstructure assembled by nano-sheets |
| CN103626220B (en) * | 2013-11-19 | 2015-04-22 | 陕西科技大学 | Method for preparing carbon-doped zinc oxide microsphere with multilevel structure |
| CN106582621B (en) * | 2016-12-29 | 2020-03-03 | 浙江光之媒新材料有限公司 | Hollow titanium dioxide loaded with metal platinum and preparation method thereof |
| CN109589917B (en) * | 2018-12-07 | 2021-10-26 | 南京理工大学 | Solid phase micro-extraction fiber based on double-layer hollow zinc oxide/carbon material and preparation method thereof |
| CN114180634B (en) * | 2020-09-15 | 2023-06-13 | 海安南京大学高新技术研究院 | ZnMnO with cage-shaped structure 4 Preparation process of nano sensing material |
| CN114264805A (en) * | 2021-12-06 | 2022-04-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of SERS enhancement-based probe, product and application thereof |
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